JPH0539417A - Colored polyarylene sulfide resin composition - Google Patents

Abstract

PURPOSE:To obtain a white fiber-reinforced polyarylene resin sulfide resin composition, capable of suppressing deterioration in mechanical properties due to toning and excellent in the mechanical properties. CONSTITUTION:A colored polyarylene sulfide resin composition is characterized in that (A) 100 pts.wt. polyarylene sulfide resin is blended with (B) 5-200 pts.wt. fibrous filler and (C) 0.05-5 pts.wt. zinc sulfide as a pigment.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a colored polyarylene sulfide resin composition having improved mechanical strength.

[0002]

2. Description of the Related Art In recent years,
BACKGROUND ART For electric / electronic device component materials, automobile device component materials, and chemical device component materials, flame-retardant thermoplastic resins having high heat resistance and chemical resistance have been required. Polyphenylene sulfide (hereinafter abbreviated as PPS)
Polyarylene sulfide represented by (hereinafter PAS
Resin is also one of the resins that meet this requirement, and PA in particular contains an inorganic fibrous reinforcing agent such as glass fiber.
The S resin composition has excellent mechanical strength and has a good ratio of physical properties to cost, and thus the demand is increasing. Recently, as this resin has spread to the market, in addition to its functions such as mechanical properties, heat resistance, and chemical resistance, the appearance of molded products has been adjusted, whiteness has been improved to facilitate identification and improve light reflection performance. There is a demand for colored products having various color tones. In particular, the white pigment is a pigment that is indispensable for the toning as a component of the composite pigment, not only when it is toned to white but also when it is toned to other tones. Titanium oxide is well known as a white pigment generally used for such a purpose. Titanium oxide has an excellent hiding power and exhibits a very clear whiteness even in a small amount, so it is exclusively used in PAS resins. However, when titanium oxide is added to a PAS resin, especially a fiber-reinforced PAS resin, an undesirable phenomenon that mechanical strength such as tensile strength, tensile elongation, bending strength and impact strength of a molded product is significantly impaired and lowered. In particular, it has a strong demand for tensile elongation and impact strength.
Such obstacles in AS resin molded products limit their applications, and their improvement is strongly desired. As an inorganic substance imparting a white color tone, there are many metal carbonates, sulfates, oxides and the like other than titanium oxide, and white toning is possible to some extent, but these inorganic substances have a hiding power. Inferior,
It is necessary to add an extremely large amount compared to titanium oxide,
As a result, mechanical properties were adversely affected, and in many cases, depending on the color tone, color adjustment was impossible regardless of the addition amount. For these reasons, it is desired to develop a white pigment having a necessary and sufficient hiding power and having little deterioration in mechanical properties. An object of the present invention is to provide a white fiber-reinforced PAS resin composition having excellent mechanical properties, which suppresses the deterioration of mechanical properties due to the toning.

[0003]

In view of such a situation, the present inventors have considered that the present invention does not impair the mechanical properties of PAS resin like titanium oxide, and has a large hiding power and sufficient coloring even in a small amount. As a result of diligent studies on a white pigment having a toning effect, it has been found that zinc sulfide is particularly effective in the fiber-reinforced PAS resin composition among many white inorganic substances and pigments, and the present invention is completed. Came to.
That is, the present invention is characterized in that (A) 100 parts by weight of PAS resin, (B) 5 to 200 parts by weight of a fibrous filler, and (C) 0.05 to 5 parts by weight of zinc sulfide as a pigment. Is a colored PAS resin composition.

The PAS resin as the component (A) in the composition of the present invention is mainly composed of repeating units (-Ar-S-) (however,
Ar is an arylene group). Examples of the arylene group (-Ar-) include p-phenylene group and m-
Phenylene, o- phenylene group, substituted phenylene group (wherein the substituent is an alkyl group, preferably an alkyl group of C ₁ -C _5, or a phenyl group), p, p'-di polyphenylene sulfone groups, p, p' A biphenylene group, a p, p'-diphenylene ether group, a p, p'-diphenylene carbonyl group, a naphthalene group and the like. In this case, in the arylene sulfide group composed of the above arylene group, a polymer using the same repeating unit, that is, a homopolymer can be used, and from the viewpoint of processability of the composition, different repeating units are used. In some cases, the included copolymers are preferred. As the homopolymer, a substantially linear PPS having a p-phenylene sulfide group as a repeating unit and using a p-phenylene group as an arylene group is particularly preferably used. In addition, as the copolymer, a combination of two or more different arylene sulfide groups among the above-mentioned arylene groups can be used.
Among them, a combination mainly containing a p-phenylene sulfide group and containing an m-phenylene sulfide group is particularly preferably used. Among them, substantially linear ones containing 60 mol% or more, more preferably 70 mol% or more of p-phenylene sulfide group are suitable from the viewpoint of physical properties such as heat resistance, moldability and mechanical properties. In this case, the repeating units of the components are contained in a block form rather than a random form (for example, those described in JP-A-61-122828).
However, it has good workability, and also has excellent heat resistance and mechanical properties, and can be preferably used. Such a polymer is generally obtained as a part of a high molecular weight polymer having a substantially linear structure obtained by polycondensation from a bifunctional monomer by a method disclosed in JP-A-617332 or JP-A-61-166720, or a part of the monomer. A crosslinked PAS resin obtained by mixing and using monomers having three or more functional groups in combination, or a compounded resin obtained by blending the crosslinked PAS resin with the above linear polymer can also be used, which is preferable. However, low molecular weight (eg at 310 ° C
PAS of 150 poise or less) or PAS that is thickened by oxidatively or thermally crosslinking it is unstable in color tone and has a blackish brown color. However, it is not preferable as a material.

As the fibrous filler as the component (B) used in the composition of the present invention, any filler can be used as long as it is a filler generally used for thermoplastic resins. For example, glass fiber, asbestos fiber, carbon fiber, silica fiber, silica-alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, potassium titanate fiber, aluminum borate fiber, and further stainless steel, aluminum, titanium, copper. Inorganic fibrous substances such as metallic fibrous substances such as brass. A particularly representative fibrous filler is glass fiber or carbon fiber. Note that high-melting-point organic fibrous substances such as polyamide, fluororesin, and acrylic resin can also be used. These fibrous fillers can be used in combination of two or more kinds. The amount of such fibrous filler used is generally 5 to 200 per 100 parts by weight of the PAS resin.
A weight part is desirable, and if it is less than that, the effect as a reinforcing material is small and the mechanical properties and heat distortion temperature are low, which is not preferable. Also, if it exceeds 200 parts by weight, the melt viscosity at the time of molding will be high, and the resulting molded product will have a strong orientation due to the fiber
It is not preferable because the anisotropy of mechanical properties becomes too high. It is preferably 10 to 150 parts by weight. In order to improve the mechanical strength of the composition, these fillers are preferably treated with a sizing agent or a surface treatment agent in advance. Examples of the treating agent include epoxy compounds, isocyanate compounds, silane compounds, titanate compounds and the like.

The zinc sulfide as the component (C) in the composition of the present invention is a white powder, which is naturally produced as sphalerite. Alternatively, it can be prepared by reacting a zinc sulfate solution or a zinc salt solution of acetic acid with ammonium sulfide or hydrogen sulfide. In the present invention, both a natural product and a synthetic product can be used, and particularly for the purpose of the present invention, a product having a high whiteness, a high relative refractive index and a high hiding power is desirable. It is preferably in the form of fine particles. Among them, the average particle diameter is preferably 10 μm or less, preferably 5 μm or less, and more preferably 2 μm or less. The amount of zinc sulfide added is preferably 0.05 to 5 parts by weight with respect to 100 parts by weight of the PAS resin, and less than 0.05 parts by weight is not desirable because the effect of hiding the hue of the resin as a white pigment is small. If so, the mechanical properties are deteriorated and the object of the present invention cannot be achieved, which is not desirable. Particularly, the addition amount, which is a feature of the present invention, in which the whiteness and the mechanical properties are well balanced, is in the range of 0.1 to 4 parts by weight.
The reason why such a zinc sulfide has a strength retaining effect not found in titanium oxide and the like, especially in a composition composed of a PAS resin and a fibrous reinforcing material, is not sufficiently clear, but it is remarkable in a coexisting system with the fibrous reinforcing material. From the above, it is understood that it exhibits some interaction with the reinforcing material.

Next, in the composition of the present invention, a particulate filler and / or a plate-like filler (D) can be used depending on the purpose, although it is not an essential component. By mixing these, the mechanical properties are balanced, and it is particularly effective for preventing warpage and deformation due to the fibrous filler. Among them, powdery and granular fillers include carbon black, silica, quartz powder, glass beads, glass powder, calcium silicate, aluminum silicate, kaolin, talc, clay, diatomaceous earth, wollastonite and other silicates. Salts, iron oxides, zinc oxide, oxides of metals such as alumina, calcium carbonate,
Examples thereof include metal carbonates such as magnesium carbonate, calcium sulfates, metal sulfates such as barium sulfate, silicon carbide, silicon nitride, boron nitride, and various metal powders. Examples of the plate-shaped filler include mica, glass flakes, various metal foils and the like. These fillers are 1
They may be used alone or in combination of two or more. Similar to the component (B), these fillers are preferably treated in advance with a sizing agent or a surface treatment agent in order to improve the mechanical strength of the composition. Examples of the treating agent include epoxy compounds, isocyanate compounds, silane compounds, titanate compounds and the like.
The amount of the particulate filler and / or the plate-like filler of the component (D) used is 5 to 200 parts by weight, preferably 150 parts by weight or less, per 100 parts by weight of the PAS resin. If it is too large, the moldability is impaired and the toughness is lowered, which is not preferable.

If necessary, a pigment or dye other than zinc sulfide is added to the composition of the present invention for toning,
It can be prepared in any color tone. In addition, known substances generally added to thermoplastic resins, that is, various stabilizers,
An antistatic agent, a flame retardant, a lubricant, a crystallization accelerator, a crystal nucleating agent and the like can be appropriately added if necessary.

The resin composition of the present invention can be prepared by the equipment and method generally used for preparing synthetic resin compositions. That is, the necessary components can be mixed, kneaded using a uniaxial or biaxial extruder, and extruded to obtain molding pellets.

Regarding the method of adding zinc sulfide, in addition to adding the resin and other components to the extruder and melt-kneading, the resin composition pellets and zinc sulfide are mixed,
For example, a method of directly attaching zinc sulfide to the surface of resin pellets, or a method of forming a high-concentration masterbatch pellet, and mixing and forming it before forming to obtain a molded product with the desired color tone. May be.

The material pellets thus obtained can be made into a desired molded article by using a generally known molding method of a thermoplastic resin such as injection molding, extrusion molding, vacuum molding, compression molding and the like. Most preferred is injection molding.

[0012]

【Example】

Examples 1 to 7 and Comparative Examples 1 to 8 As shown in Table 1, as a component (A), polyphenylene sulfide resin (PPS) (Kureha Chemical Industry Co., Ltd., trade name “Fortron KPS”) Zinc sulfide as an ingredient) was added as shown in Table 1 and mixed for 2 minutes with a Henschel mixer. Next, the fibrous filler as the component (B) is added in the amount shown in Table 1, and the powdered inorganic filler as the component (D) is added in the amount shown in Table 1 as needed.
Mix for 30 seconds. This was melt-kneaded with an extruder having a cylinder temperature of 310 ° C. to prepare pellets of the polyphenylene sulfide resin composition. Using these pellets, cylinder temperature 320 ℃, mold temperature 150 ℃, injection molding machine, ASTM
The test piece was molded and the tensile strength, tensile elongation, bending strength, bending elastic modulus, and Izod impact strength were measured. Further, a 5 mm × 5 mm × 2 mmt flat plate was molded under the same molding conditions, and the whiteness L value was measured using a color difference meter Z-300A manufactured by Nippon Denshoku. For comparison, the same test was conducted in the case where no pigment was added and the case where ordinary titanium oxide was added as a white pigment instead of zinc sulfide (C). The results are shown in Table 1.

[0013]

[Table 1]

[0014]

As is apparent from the above description and Examples, the colored PAS resin composition using zinc sulfide of the present invention is
As compared with a PAS resin composition using a conventional white coloring pigment such as titanium oxide, the whiteness is equivalently high, and a molded product having remarkably improved mechanical properties, which has been a defect in the past, can be obtained. Therefore, it can be adjusted to any color with a pigment without impairing the physical properties, and it is effective for the purpose of adjusting the appearance and identifying the parts. Highly tough colored PA that prevents press-fit cracking
Used as an S resin composition.

Claims (3)

[Claims] 1. A polyarylene sulfide resin (A) 1
A colored polyarylene sulfide resin composition comprising (B) 5 to 200 parts by weight of (B) a fibrous filler, and 0.05 to 5 parts by weight of zinc sulfide as a pigment. 2. The polyarylene sulfide resin composition according to claim 1, wherein the fibrous filler (B) is glass fiber. 3. A particulate filler and / or as the component (D)
Alternatively, the plate-like filler may be added in an amount of 5 to 2 per 100 parts by weight of the component (A).
The compounding amount is 00 parts by weight,
The polyarylene sulfide resin composition described.